CN106684254A - Organic electroluminescent device containing chemical compound with dibenzocycloheptene as its core and the application thereof - Google Patents

Organic electroluminescent device containing chemical compound with dibenzocycloheptene as its core and the application thereof Download PDF

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CN106684254A
CN106684254A CN201611206415.XA CN201611206415A CN106684254A CN 106684254 A CN106684254 A CN 106684254A CN 201611206415 A CN201611206415 A CN 201611206415A CN 106684254 A CN106684254 A CN 106684254A
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唐丹丹
李崇
叶中华
张兆超
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Jiangsu Sanyue Optoelectronic Technology Co Ltd
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
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    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
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    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene

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Abstract

The invention discloses an organic electroluminescent device containing a chemical compound with dibenzocycloheptene as its core and the application thereof. The device comprises a hole transport layer, a light emitting layer, and an electron transport layer. The composing material for the light emitting layer contains a chemical compound with dibenzocycloheptene as its core. The optimized dibenzocycloheptene structure used by the chemical compound material matches the branched-chain structures represented by the formula 2, formula 3 and formula 4 to conveniently realize the energy transmission between the subject material and the object material so as to obtain the high efficiency of the device more easily. In addition, the chemical compound of the invention possesses relatively high glass transition temperature and molecular thermal stability as well as a proper HOMO and LUMO energy grade. With the optimization of the device structure, it is possible to effectively raise the optical performance and the service life of an OLED device.

Description

A kind of organic electroluminescence of the compound containing with dibenzocycloheptene as core Part and its application
Technical field
The present invention relates to technical field of semiconductors, is with dibenzocycloheptene as core more particularly, to a kind of emitting layer material The organic electroluminescence device of heart compound and its application.
Background technology
Organic electroluminescent (OLED:Organic Light Emission Diodes) device technology both can be used to make Make new display product, it is also possible to for making novel illumination product, be expected to substitute existing liquid crystal display and fluorescent lighting, Application prospect is quite varied.
OLED luminescent devices are just as the structure of sandwich, including electrode material film layer, and be clipped in Different electrodes film layer it Between organic functional material, various difference in functionality materials are overlapped mutually according to purposes and collectively constitute together OLED luminescent devices. As current device, when the two end electrodes applied voltage to OLED luminescent devices, and by electric field action organic layer functional material Positive and negative charge in film layer, positive and negative charge is further combined in luminescent layer, that is, produce OLED electroluminescent.
Currently, OLED Display Techniques are applied in fields such as smart mobile phone, panel computers, further will also be to electricity Depending on etc. the extension of large scale application, but, require to compare with the products application of reality, the luminous efficiency of OLED is used The performances such as life-span also need to further lifting.
Include for OLED luminescent devices propose high performance research：The driving voltage of device is reduced, the luminous of device is improved Efficiency, improves service life of device etc..In order to realize the continuous lifting of the performance of OLED, not only need from OLED The innovation of structure and processing technology, with greater need for constantly research and the innovation of oled light sulfate ferroelectric functional material, formulates out higher performance OLED Functional material.
Being applied to the oled light sulfate ferroelectric functional material of OLED can be divided into two big class, i.e. electric charge injection transmission from purposes Material and luminescent material, further, can also inject charge into transmission material and be divided into electron injection transmission material, electronic blocking material Material, hole injection transmission material and hole barrier materials, can also be divided into main body luminescent material and dopant material by luminescent material.
In order to make high performance OLED luminescent devices, it is desirable to which various organic functional materials possess good photoelectric characteristic, For example, as charge transport materials, it is desirable to good carrier mobility, high-vitrification conversion temperature etc., as luminous The material of main part of layer requires that material has good bipolarity, appropriate HOMO/LUMO energy ranks etc..
Constituting the oled light sulfate ferroelectric functional material film layer of OLED at least includes two-layer above structure, applies in industry OLED structure, then pass including hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electronics Various film layers such as defeated layer, electron injecting layer, that is to say, that the photoelectric functional material for being applied to OLED is noted including at least hole Enter material, hole mobile material, luminescent material, electron transport material etc., material type and collocation form have rich and many The characteristics of sample.In addition, for the OLED collocation of different structure, the photoelectric functional material for being used has stronger Selectivity, performance of the identical material in different structure device, it is also possible to completely totally different.
Therefore, for the industry application requirement of current OLED, and the difference in functionality film layer of OLED, device Photoelectric characteristic demand, it is necessary to which selection is more suitable for, and with high performance OLED functional materials or combination of materials, could realize device The overall characteristic of high efficiency, long-life and low-voltage.For the actual demand that current OLED shows Lighting Industry, current OLED The development of material is also far from enough, lags behind the requirement of panel manufacturing enterprise, used as the organic of material enterprise development higher performance Functional material is particularly important.
The content of the invention
For the problems referred to above that prior art is present, the invention provides one kind is with dibenzocycloheptene as core compound Organic electroluminescence device and its application as emitting layer material.The compounds of this invention contains dibenzocycloheptene structure, tool There are higher vitrification point and molecule heat stability, suitable HOMO energy levels, can be applied to as luminescent layer dopant material On machine light emitting diode, and screen known materials and carry out each functional layer collocation and combination, Combination nova collocation device has good Photoelectric properties, disclosure satisfy that the demand of OLED enterprise, particularly OLED display panel and OLED Illumination Enterprises.
Technical scheme is as follows：
A kind of organic electroluminescence device of the compound containing with dibenzocycloheptene as core, the device includes hole Transport layer, luminescent layer, electron transfer layer, the device emitting layer material includes the compound containing dibenzocycloheptene for core, Shown in the structural formula of compound such as formula (1)：
In formula (1), R1、R2Independently be expressed as substituted or unsubstituted C6-40Aryl, substituted or unsubstituted 3 One kind of yuan of rings to 40 membered ring heteroaryls；R1With R2Between dotted line represent R1With R2Cyclization or not cyclization can be connected；R1、R2Phase It is same or different；
R3、R4Independently be expressed as formula (2), formula (3) or structure shown in formula (4)；
In formula (2), R5、R6Separately it is expressed as substituted or unsubstituted C6-40Aryl, substituted or unsubstituted 3 One kind in yuan of rings to 40 membered ring heteroaryls；R5、R6Identical or difference；
In formula (4), X1It is expressed as oxygen atom, sulphur atom, C1-10Alkylidene, C that straight chained alkyl replaces1-10Branched alkyl One kind in the tertiary amine groups that alkylidene, alkyl-substituted tertiary amine groups or the aryl that substituted alkylidene, aryl replace replaces；
In formula (3) and formula (4), R7、R8Independently be expressed as hydrogen atom or structure shown in formula (5)；
Wherein, a is selected fromX2、X3Independently be expressed as oxygen atom, sulphur atom, C1-10Directly Alkylidene, C that alkyl group replaces1-10Alkylidene, alkylidene, the alkyl-substituted tertiary amine groups of aryl replacement that branched alkyl replaces Or the one kind in the tertiary amine groups of aryl replacement；Structure shown in formula (5) passes through CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL4- CL5Key, CL‘1-CL’2Key, CL‘2-CL’3Key, CL‘3-CL’4Key or CL‘4-CL’5Key and formula (3) or formula (4) connection.
Preferably, R in the formula (1)1、R2With R in formula (2)5、R6Structure being expressed as independently：
In any one.
Preferably, the representation of the formula (3) is：
In any one.
Preferably, the representation of the formula (4) is：
Any one.
Preferably, it is characterised in that the concrete structure formula of the compound is：
In any one.
The applicant additionally provides described with dibenzocycloheptene as core compound preparation method：
Work as R3And R4When identical, with following reaction equation：
Specifically include following steps：1) by intermediate compound I and R3- H toluene dissolves, wherein, the intermediate compound I and R3- H's Mol ratio is 1:(2.0~3.0)；
2) Pd is added in above-mentioned reaction system2(dba)3, tri-butyl phosphine, sodium tert-butoxide；The Pd2(dba)3With in The mol ratio of mesosome I is (0.006~0.02):1, the mol ratio of the tri-butyl phosphine and intermediate compound I for (0.006~ 0.02):1, the sodium tert-butoxide is (3.0~5.0) with the mol ratio of intermediate compound I:1；
3) under the protection of noble gases, above-mentioned mixed solution reacts under 95~110 DEG C of temperature conditionss 10~ 24h, naturally cools to room temperature, filtering reacting solution, and filtrate is rotated to solvent-free, crosses neutral silica gel post, obtains target product；
Work as R3And R4When differing, with following reaction equation：
Specifically include following steps：1) by intermediate compound I and R3- H toluene dissolves, wherein, the intermediate compound I and R3- H's Mol ratio is 1:(1.2~2.0)；
2) Pd is added in the reaction system in 1)2(dba)3, tri-butyl phosphine, sodium tert-butoxide；；The Pd2(dba)3With The mol ratio of intermediate compound I is (0.006~0.02):1, the mol ratio of the tri-butyl phosphine and intermediate compound I for (0.006~ 0.02):1, the sodium tert-butoxide is (2.0~3.0) with the mol ratio of intermediate compound I:1；
3) under the protection of noble gases, above-mentioned mixed solution reacts under 95~110 DEG C of temperature conditionss 10~ 24h, naturally cools to room temperature, and filtering reacting solution, and filtrate is rotated to solvent-free, crosses neutral silica gel post, obtains intermediate product；
4) by intermediate product and R4- H toluene dissolves, wherein, the intermediate product and R4The mol ratio of-H is 1:(1.2~ 2.0)；
5) Pd is added in the reaction system in 4)2(dba)3, tri-butyl phosphine, sodium tert-butoxide；The Pd2(dba)3With The mol ratio of intermediate product is (0.006~0.02):1, the mol ratio of the tri-butyl phosphine and intermediate product for (0.006~ 0.02):1, the sodium tert-butoxide is (2.0~3.0) with the mol ratio of intermediate product:1；
6) under the protection of noble gases, above-mentioned mixed solution reacts under 95~110 DEG C of temperature conditionss 10~ 24h, naturally cools to room temperature, and filtering reacting solution, and filtrate is rotated to solvent-free, crosses neutral silica gel post, obtains target product.
The organic electroluminescence device that the applicant provides also includes hole injection layer, hole transmission layer, luminescent layer, electronics Transport layer, electron transfer layer, the emitting layer material of the organic electroluminescence device includes the change with dibenzocycloheptene as core Compound.
Preferably, the dopant material using dibenzocycloheptene as core compound as luminescent layer；The luminescent layer Material of main part be the compound containing anthryl, shown in the structure such as formula (6) of the compound containing anthryl：
In formula (6), B1-B8Independently be expressed as hydrogen atom, C1-30Alkyl or alkane that straight or branched alkyl replaces Epoxide, substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 3 yuan of rings are to 30 membered ring heteroaryls；B9、B10Independently table It is shown as substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 3 yuan to 30 unit's heteroaryls.Formula (6) preferred structure formula is： In Any one.
Preferably, the material of the hole transmission layer is the compound containing triarylamine group, described to contain triaryl Shown in the structure of the compound of amine groups such as formula (7)：
In formula (7), D1-D3The substituted or unsubstituted C of expression independently6-30Aryl, substituted or unsubstituted 3 yuan Ring is to 50 membered ring heteroaryls；D1-D3Identical or difference.Formula (7) preferred structure formula is：
In it is any It is a kind of.
Preferably, the material of the electron transfer layer is in general formula (8), (9), (10), (11), material shown in (12) One kind：
E in formula (8), formula (9), formula (10), formula (11), formula (12)1-E10It is respectively and independently selected from hydrogen, C1-30 Alkyl or alkoxyl, substituted or unsubstituted C that straight or branched alkyl replaces6-40Aryl, substituted or unsubstituted 3 yuan of rings are extremely 30 membered ring heteroaryls, and E1-E10It is asynchronously hydrogen.
Wherein, the preferred structure formula of formula (8) is：
Formula (9) the preferred structure formula is：
Formula (10) the preferred structure formula is：
Formula (11) the preferred structure formula is：
Formula (12) the preferred structure formula is：
Preferably, the hole injection layer material is in having structure formula (13), (14), material shown in (15) Kind：
In formula (13), F1-F3The substituted or unsubstituted C of expression independently6-30Aryl, substituted or unsubstituted 3 yuan To 30 unit's heteroaryls；F1-F3Identical or difference.
In formula (14), formula (15), G1-G6Expression hydrogen independently, itrile group, halogen, amide groups, alkoxyl, ester Base, nitro, C1-30Carbon atom, substituted or unsubstituted C that straight or branched alkyl replaces6-30Aryl, 3 yuan of rings are miscellaneous to 30 yuan of rings Aryl and G1-G6It is asynchronously hydrogen.
Wherein, formula (13) preferred structure formula is：
Formula (14) the preferred structure formula is：
Formula (15) the preferred structure formula is：
Preferably, the electron injecting layer material is the one kind in lithium, lithium salts or cesium salt.Wherein described lithium salts is 8- hydroxyl quinolines One kind in quinoline lithium, lithium fluoride, lithium carbonate or Lithium Azide；The cesium salt is in cesium fluoride, cesium carbonate or cesium azide Kind.
The applicant additionally provides a kind of application of the organic electroluminescence device, and it is used to prepare OLED illuminations or aobvious Show panel.The present invention is beneficial to be had technical effect that：
Traditional stilbene aryl blue emitting material there are problems that in solid-state, cause glow peak to become Width, spectral red shift, fluorescence quantum efficiency decline.So, typically they are entrained in certain current-carrying in the way of low concentration In the main body of sub- property, even if low concentration doping, obtained device external quantum efficiency only has 2-3%, material hexichol of the present invention And double bond cyclization is reduced the probability of compound crystal by cycloheptene, and the glass transition temperature of compound is improve again, is kept away Exempt from intermolecular aggregation, it is easy to accomplish energy transmission between Subjective and Objective material, and in high-dopant concentration, be not likely to produce Efficiency declines, it is easy to obtain the high efficiency of device.The presence of double bond in mother nucleus structure is also material of the present invention in device application Produce long-life principal element.Material of the present invention introduces the diaryl-amine base electron donor with hole transport performance in side chain, N is generally connected with, the pi-conjugated system of N- diaryl-amine base electron donors is all the blue light material with high fluorescence quantum efficiency.
The compound using dibenzocycloheptene as core as OLED luminescent devices dopant material when, the electricity of device Stream efficiency, power efficiency and external quantum efficiency are greatly improved；Lifted clearly simultaneously for device lifetime.Enter one Step, in the collocation of OLED Rotating fields, after introducing hole and electron injecting layer, make transparent anode, metallic cathode and organic Material interface is more stable, hole, electron injection effect promoting；Hole transmission layer again can lamination be two-layer or multilamellar, adjoin The hole transmission layer of luminescent layer side can be named as electronic barrier layer (EBL) again, there is provided electronic blocking is acted on, and is made in luminescent layer Exciton combined efficiency is lifted, and the hole transmission layer of adjacent hole injection layer side then plays hole transport and reduces exciton transfer wall The effect at base；Electron transfer layer again can lamination be two-layer or multilamellar, the electron transfer layer of adjacent luminescent layer side can be named again For hole blocking layer (HBL), there is provided hole barrier is acted on, exciton combined efficiency in luminescent layer is lifted, adjoin electron injecting layer The electron transfer layer of side then plays a part of electric transmission and reduces exciton transfer barrier.It should be mentioned, however, that in these layers Be each not necessarily present.
The combined effect of OLED compound of the present invention：So that the driving voltage of device is reduced, current efficiency, work( Rate efficiency, external quantum efficiency are further enhanced, and it is obvious that device lifetime lifts effect.Have in OLED luminescent devices good Application effect, with good industrialization prospect.Make us against expectation, it has been found that, it is more particularly described hereinafter Compound is combined and realizes this purpose, and causes the improvement of organic electroluminescence device, particularly voltage, efficiency and life-span Improvement.This is particularly well-suited to the electroluminescent device of blue-fluorescence, especially in the device architecture and material using the present invention During combination, situation is such.
Description of the drawings
Fig. 1 is the materials application cited by the present invention in the structural representation of OLED；
Wherein, 1, transparent substrates, 2, ito anode layer, 3, hole injection layer (HIL), 4, hole transmission layer (HTL), 5, electricity Sub- barrier layer (EBL), 6, luminescent layer (EML), 7, hole blocking layer (HBL), 8, electron transfer layer (ETL), 9, electron injecting layer (EIL), 10, negative electrode reflection electrode layer.
Specific embodiment
Embodiment 1：Intermediate compound I based on mother nucleus structure and the synthesis based on the branched structure intermediate II in formula (2)
A. it is based on the synthesis of the intermediate compound I of mother nucleus structure：Work as R1With R2During not connected cyclization, intermediate compound I is synthesized:
Above-mentioned preparation method is specifically comprised the following steps：
1)R1- Br and magnesium powder are raw material, the R1- Br and magnesium powder molar ratio are 1:1, add tetrahydrofuran, nitrogen atmosphere Under, 70 DEG C are heated to, back flow reaction 3-5 hour is remaining without magnesium powder, and reaction is complete, generates grignard reagent；The above-mentioned tetrahydrochysene The consumption of furan is preferably 1gR1- Br adds 3-6ml tetrahydrofurans,
2) raw material U is weighedIn being dissolved in tetrahydrofuran, the raw material U and R1- Br mol ratios are 1: 1, then Deca step 1) grignard reagent for preparing, after completion of dropwise addition, 60-70 DEG C is heated to, back flow reaction 10-25 hour is raw Into the form salt precipitation of a large amount of whites, reaction terminates, then Deca saturation NHCl4Solution, by the form salt tertiary alcohol is converted into； Again extract is obtained with ether extraction, then the extract anhydrous sodium sulfate drying rotates desolventizing to without fraction, obtain Tertiary alcohol crude product, gained tertiary alcohol crude product petroleum ether：Dichloromethane mixed solvent crosses neutral silica gel post, obtains the solid tertiary alcohol Compound；Preferably above-mentioned petroleum ether：The volume ratio 3 of dichloromethane:2；Step 2) in the tetrahydrofuran consumption it is preferred It is that every 1g raw materials U is dissolved in 4-8ml tetrahydrofurans；The consumption of the ether is 1g tert-alcoholsAdd 5- In 10ml ether.
3) by 1:2 equivalents weigh solid tert-alcoholsAnd R2- H, in being dissolved in dichloromethane, described two The consumption of chloromethanes is dissolved in 5-8ml dichloromethane for 1g solid tertiary alcohol pure compounds, and again Deca is borontrifluoride under room temperature condition Diethyl etherate, the solid tert-alcohols are 1 with boron trifluoride etherate molar ratio:1.5, reaction 30-60 minutes, it is subsequently adding ethanol and water quenching is gone out reaction, then extracted with dichloromethane, anhydrous sodium sulfate drying, rotates precipitation To without fraction, petroleum ether crosses neutral silica gel post, ethanol for agent：Dichloromethane mixed solvent recrystallization, obtains intermediate compound IPreferably, the ethanol：Ethanol and methylene chloride volume compare 1 in dichloromethane mixed solvent:1.
When R1 is connected cyclization with R2, intermediate compound I is synthesized：
Weigh a bromo-derivative Br-R1-R2In being dissolved in tetrahydrofuran, -78 DEG C are cooled to, then it is being added dropwise over 2.5mol/L just The hexane solution of butyl lithium, after completion of dropwise addition, reacts 30 minutes, then to Deca in reaction system at a temperature of -78 DEG C Raw material UTetrahydrofuran solution, after completion of dropwise addition, be warmed to room temperature, react 10-15h, reaction terminate after, drop Plus saturated sodium bicarbonate solution；Again extract is obtained with dichloromethane extraction, the extract is dried with anhydrous magnesium sulfate, then Revolving desolventizing obtains tertiary alcohol product to without fraction, and the consumption of the tetrahydrofuran is preferably 1g Br-R1-R2Add 10-15ml Tetrahydrofuran, per 1g raw material U 4-8ml tetrahydrofurans are dissolved in；The n-BuLi and the Br-R1-R2Mol ratio is 1:1, it is described The raw material U and Br-R1-R2Mol ratio is 1:1, the consumption of the dichloromethane is that 1g tert-alcohols add 5-10ml ether In.
Solid tertiary alcohol product is dissolved in acetic acid, the hydrochloric acid solution of 12mol/L is added, 90-110 DEG C is heated to, reaction 30 Minute, room temperature is cooled to, extract is obtained with dichloromethane extraction, the extract is dried with anhydrous magnesium sulfate, is then rotated Desolventizing obtains intermediate compound I crude product to without fraction, and intermediate compound I crude product crosses neutral silica gel post, ethanol：Dichloromethane mixes Solvent recrystallization, obtains intermediate compound IPreferably, the ethanol：Ethanol and two in dichloromethane mixed solvent Chloromethanes volume ratio 1:1.The consumption of the acetic acid is preferably 1g solid tertiary alcohols product and adds 5-8ml acetic acid；The 12mol/L's Hydrochloric acid solution and tertiary alcohol product molar ratio are (0.04-0.06):1.
When R1 and R2 are not connected to cyclization, by taking the synthesis of intermediate A 1 as an example：
1) there-necked flask of 250ml, under the atmosphere for being passed through nitrogen, adds 0.05mol bromobenzenes and 0.05mol Mg powder, 60ml Tetrahydrofuran, is heated to 70 DEG C, and back flow reaction 4 hours is remaining without magnesium powder, and reaction is complete, generates grignard reagent；The three of 250ml Mouth bottle, under the atmosphere for being passed through nitrogen, adds 0.05mol3, the bromo- 5- dibenzosuberenones of 7- bis-, the stirring of 50ml tetrahydrofurans Dissolving, the above-mentioned grignard reagent of Deca, 60 DEG C are reacted 24 hours, generate a large amount of white precipitates, are eventually adding saturation NHCl4By form Salt is converted into alcohol；After completion of the reaction, ether extraction, is dried revolving, petroleum ether：Dichloromethane mixed solvent (3:2) silicagel column is pure Change, obtain the solid tertiary alcohol of yellowish, HPLC purity 99.2%, yield is 83.2%；
Elementary analysiss structure (molecular formula C21H14Br2O)：Theoretical value C, 69.44；H,4.16；Br,22.00；O,4.40；Survey Examination value：C,69.42；H,4.15；Br,22.01；O,4.42.HPLC-MS：Material molecule amount is 362.03, surveys molecular weight 362.33。
2) by 1:2 when the above-mentioned tertiary alcohols of 0.04mol and 0.08mol benzene is measured, and the stirring of 100ml dichloromethane mixes, in room temperature Under the conditions of Deca 8ml boron trifluoride etherate, react 30 minutes, add 20ml ethanol and 20ml water quenchings to go out reaction, use Dichloromethane (20ml*3) is extracted, and is dried revolving, and petroleum ether silica column purification uses ethanol：Dichloromethane (volume ratio 1:1) tie again Crystalline substance, obtains intermediate A 1, and HPLC purity 99.5%, yield is 75.5%；Elementary analysiss structure (molecular formula C27H18Br2)：It is theoretical Value C, 64.57；H,3.61；Br,31.82；Test value：C,64.56；H,3.63；Br,31.81.
HPLC-MS：Material molecule amount is 499.98, surveys molecular weight 500.15.
When R1 is connected cyclization with R2, by taking the synthesis of intermediate B 1 as an example：
The there-necked flask of 250ml, under the atmosphere for being passed through nitrogen, adds 0.05mol4- bromo- 1,1 '-biphenyl, 50ml tetrahydrochysene furans Dissolving of muttering is complete, is cooled to -78 DEG C, the hexane solution of 0.05mol2.5mol/L n-BuLis is added dropwise over, at -78 DEG C Reaction 30 minutes, then to Deca 0.05mol3 in reaction system, the tetrahydrofuran solution of the bromo- 5- dibenzosuberenones of 7- bis- (30ml) reaction 12h, is warmed to room temperature, saturated sodium bicarbonate solution is eventually adding and is quenched；Dichloromethane is extracted, and is dried revolving to nothing Fraction obtains the intermediate product tertiary alcohol.Then the 0.02mol intermediate product tertiary alcohols are weighed, in being added to 8ml acetic acid, 100 DEG C is heated to, Reaction 30 minutes, by system room temperature is down to, and dichloromethane extraction is dried revolving extremely without fraction, crude product petroleum ether silicagel column Purification, uses ethanol：Dichloromethane (volume ratio 1:1) recrystallization, obtains B1 between middle body, HPLC purity 99.6%, and yield is 71.5%；
Elementary analysiss structure (molecular formula C27H16Br2)：Theoretical value C, 64.83；H,3.22；Br,31.95；Test value：C, 64.84；H,3.20；Br,31.96.HPLC-MS：Material molecule amount is 497.96, surveys molecular weight 498.18.
B. the synthesis based on the intermediate II of branched structure in formula (2)：Synthesis：
1) by R5- Br and R6-NH2Dissolved with toluene, wherein, the R5- Br and R6-NH2Mol ratio be 1:(1.2~ 2.0)；
2) Pd is added in above-mentioned reaction system2(dba)3, tri-butyl phosphine, sodium tert-butoxide；The Pd2(dba)3With R5- The mol ratio of Br is (0.006~0.02):1, the tri-butyl phosphine and R5The mol ratio of-Br is (0.006~0.02):1, institute State sodium tert-butoxide and R5The mol ratio of-Br is (2.0~3.0):1；
3) under the protection of noble gases, above-mentioned mixed solution reacts under 95~110 DEG C of temperature conditionss 10~ 24h, naturally cools to room temperature, and filtering reacting solution, and filtrate is rotated to solvent-free, crosses neutral silica gel post, obtains target product；
As a example by choosing the synthesis of intermediate C1：
In the there-necked flask of 250ml, under leading to nitrogen protection, 0.05mol bromobenzenes, 0.06mol aniline, 150ml toluene are added Stirring mixing, is subsequently adding 0.15mol sodium tert-butoxides, and 5 × 10-4molPd2(dba)3, 5 × 10-4Mol tri-butyl phosphines, heating To 105 DEG C, back flow reaction 24 hours, sample point plate shows remaining without bromo-derivative, and reaction is complete；Naturally cool to room temperature, mistake Filter, filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains diphenylamines, and HPLC purity 99.3% is received Rate 66.8%；
Elementary analysiss structure (molecular formula C12H11N)：Theoretical value C, 85.17；H,6.55；N,8.28；Test value：C, 85.16；H,6.57；N,8.27.HPLC-MS：Material molecule amount is 169.09, surveys molecular weight 169.31.
Intermediate compound I, the concrete structure of raw material and intermediate compound I such as table needed for synthesis are prepared with the synthetic method of intermediate A 1 Shown in 1；Intermediate compound I, the such as table 2 of the concrete structure of raw material and intermediate compound I needed for synthesis are prepared with the synthetic method of intermediate B 1 It is shown；Branched structure intermediate II is prepared with the synthetic method of intermediate C1, raw material needed for synthesis and intermediate II it is concrete Structure is as shown in table 3.
Table 1
Table 2
Table 3
Embodiment 2：The synthesis of compound 1：
In the there-necked flask of 250ml, under leading to nitrogen protection, 0.01mol intermediate A 1,0.024mol intermediate C1 are added, The stirring mixing of 150ml toluene, is subsequently adding 0.04mol sodium tert-butoxides, and 1 × 10-4molPd2(dba)3, 1 × 10-4The tertiary fourths of mol tri- Base phosphine, is heated to 105 DEG C, and back flow reaction 24 hours, sample point plate shows remaining without bromo-derivative, and reaction is complete；Naturally cool to Room temperature, filters, and filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains target product, HPLC purity 99.5%, yield 66.8%；
Elementary analysiss structure (molecular formula C51H38N2)：Theoretical value C, 90.23；H,5.64；N,4.13；Test value：C, 90.24；H,5.65；N,4.11.HPLC-MS：Material molecule amount is 678.30, surveys molecular weight 678.57.
Embodiment 3：The synthesis of compound 3：
In the there-necked flask of 250ml, under leading to nitrogen protection, 0.01mol intermediate A 1,0.024mol intermediate C2 are added, The stirring mixing of 150ml toluene, is subsequently adding 0.04mol sodium tert-butoxides, and 1 × 10-4molPd2(dba)3, 1 × 10-4The tertiary fourths of mol tri- Base phosphine, is heated to 105 DEG C, and back flow reaction 24 hours, sample point plate shows remaining without bromo-derivative, and reaction is complete；Naturally cool to Room temperature, filters, and filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains target product, HPLC purity 99.7%, yield 64.4%；
Elementary analysiss structure (molecular formula C69H54N2O2)：Theoretical value C, 87.87；H,5.77；N,2.97；O,3.39；Test Value：C,87.86；H,5.76；N,2.98；O,3.40.HPLC-MS：Material molecule amount is 942.42, surveys molecular weight 942.71.
Embodiment 4：The synthesis of compound 4：
Prepare by the synthetic method of compound 1 in embodiment 2, difference is to replace intermediate C1 with intermediate C3；
Elementary analysiss structure (molecular formula C59H54N2)：Theoretical value C, 89.58；H,6.88；N,3.54；Test value：C, 89.57；H,6.87；N,3.56.HPLC-MS：Material molecule amount is 790.43, surveys molecular weight 790.68.
Embodiment 5：The synthesis of compound 13：
Prepare by the synthetic method of compound 1 in embodiment 2, difference is to replace intermediate C1 with intermediate C4；
Elementary analysiss structure (molecular formula C67H50N2O2)：Theoretical value C, 87.94；H,5.51；N,3.06；O,3.50；Test Value：C,87.95；H,5.50；N,3.04；O,3.51.HPLC-MS：Material molecule amount is 914.39, surveys molecular weight 914.66.
Embodiment 6：The synthesis of compound 18：
In the there-necked flask of 250ml, under leading to nitrogen protection, 0.01mol intermediate B 1,0.024mol intermediate C1 are added, The stirring mixing of 150ml toluene, is subsequently adding 0.04mol sodium tert-butoxides, and 1 × 10-4molPd2(dba)3, 1 × 10-4The tertiary fourths of mol tri- Base phosphine, is heated to 105 DEG C, and back flow reaction 24 hours, sample point plate shows remaining without bromo-derivative, and reaction is complete；Naturally cool to Room temperature, filters, and filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains target product, HPLC purity 99.2%, yield 64.1%；
Elementary analysiss structure (molecular formula C51H36N2)：Theoretical value C, 90.50；H,5.36；N,4.14；Test value：C, 90.52；H,5.35；N,4.13.HPLC-MS：Material molecule amount is 676.29, surveys molecular weight 676.55.
Embodiment 7：The synthesis of compound 20：
Prepare by the synthetic method of compound 18 in embodiment 6, difference is to replace intermediate C1 with intermediate C3；
Elementary analysiss structure (molecular formula C59H52N2)：Theoretical value C, 89.81；H,6.64；N,3.55；Test value：C, 89.82；H,6.64；N,3.54.HPLC-MS：Material molecule amount is 788.41, surveys molecular weight 788.73.
Embodiment 8：The synthesis of compound 23：
Prepare by the synthetic method of compound 18 in embodiment 6, difference is to replace intermediate C1 with intermediate C5；
Elementary analysiss structure (molecular formula C63H60N2)：Theoretical value C, 89.53；H,7.16；N,3.31；Test value：C, 89.52；H,7.15；N,3.33；HPLC-MS：Material molecule amount is 844.48, surveys molecular weight 844.74.
Embodiment 9：The synthesis of compound 26：
Prepare by the synthetic method of compound 1 in embodiment 2, difference is to replace intermediate C1 with intermediate C6；
Elementary analysiss structure (molecular formula C75H66N2)：Theoretical value C, 90.50；H,6.68；N,2.81；Test value：C, 90.51；H,6.67；N,2.82；HPLC-MS：Material molecule amount is 994.52, surveys molecular weight 994.83.
Embodiment 10：The synthesis of compound 35：
Prepare by the synthetic method of compound 18 in embodiment 6, difference is to replace intermediate C1 with intermediate C2；
Elementary analysiss structure (molecular formula C69H52N2O2)：Theoretical value C, 88.05；H,5.57；N,2.98；O,3.40；Test Value：C,88.06；H,5.56；N,2.97；O,3.41.HPLC-MS：Material molecule amount is 940.40, surveys molecular weight 940.68.
Embodiment 11：The synthesis of compound 36：
Prepare by the synthetic method of compound 18 in embodiment 6, difference is to replace intermediate C1 with intermediate C4；
Elementary analysiss structure (molecular formula C67H48N2O2)：Theoretical value C, 88.13；H,5.30；N,3.07；O,3.50；Test Value：C,88.12；H,5.31；N,3.06；O,3.51；HPLC-MS：Material molecule amount is 912.37, surveys molecular weight 912.61.
Embodiment 12：The synthesis of compound 37：
Prepare by the synthetic method of compound 18 in embodiment 6, difference is to replace intermediate C1 with intermediate C7；
Elementary analysiss structure (molecular formula C67H48N2O2)：Theoretical value C, 88.13；H,5.30；N,3.07；O,3.50；Test Value：C,88.11；H,5.31；N,3.06；O,3.52.HPLC-MS：Material molecule amount is 912.37, surveys molecular weight 912.65.
Embodiment 13：The synthesis of compound 39：
Prepare by the synthetic method of compound 18 in embodiment 6, difference is to replace intermediate C1 with intermediate C8；
Elementary analysiss structure (molecular formula C71H56N2O2)：Theoretical value C, 87.98；H,5.82；N,2.89；O,3.30；Test Value：C,87.97；H,5.81；N,2.90；O,3.32.HPLC-MS：Material molecule amount is 968.43, surveys molecular weight 968.74.
Embodiment 14：The synthesis of compound 44：
Prepare by the synthetic method of compound 1 in embodiment 2, difference is to replace intermediate A 1 with intermediate A 2；
Elementary analysiss structure (molecular formula C50H37N3)：Theoretical value C, 88.33；H,5.49；N,6.18；Test value：C, 88.34；H,5.47；N,6.19.HPLC-MS：Material molecule amount is 679.30, surveys molecular weight 679.67.
Embodiment 15：The synthesis of compound 49：
Prepare by the synthetic method of compound 18 in embodiment 6, difference is to replace intermediate C1 with intermediate C9；
Elementary analysiss structure (molecular formula C75H48N2O2)：Theoretical value C, 89.26；H,4.79；N,2.78；O,3.17；Test Value：C,89.25；H,4.80；N,2.79；O,3.16.HPLC-MS：Material molecule amount is 1008.37, surveys molecular weight 1008.77。
Embodiment 16：The synthesis of compound 51：
Prepare by the synthetic method of compound 20 in embodiment 7, difference is to replace intermediate B 1 with intermediate B 2；
Elementary analysiss structure (molecular formula C65H64N2)：Theoretical value C, 89.40；H,7.39；N,3.21；Test value：C, 89.41；H,7.37；N,3.22.HPLC-MS：Material molecule amount is 872.51, surveys molecular weight 872.83.
Embodiment 17：The synthesis of compound 59：
Prepare by the synthetic method of compound 18 in embodiment 6, difference is to replace intermediate C1 with intermediate C10；
Elementary analysiss structure (molecular formula C73H64N2)：Theoretical value C, 90.45；H,6.66；N,2.89；Test value：C, 90.44；H,6.68；N,2.88.HPLC-MS：Material molecule amount is 968.51, surveys molecular weight 968.86.
Embodiment 18：The synthesis of compound 71：
Prepare by the synthetic method of compound 18 in embodiment 6, difference is to replace intermediate C1 with intermediate D1；
Elementary analysiss structure (molecular formula C63H36N2O2)：Theoretical value C, 88.71；H,4.25；N,3.28；O,3.75；Test Value：C,88.70；H,4.24；N,3.30；O,3.76.HPLC-MS：Material molecule amount is 852.28, surveys molecular weight 852.55.
Embodiment 19：The synthesis of compound 81：
Prepare by the synthetic method of compound 1 in embodiment 2, difference is to replace intermediate A 1 with intermediate A 3, in Mesosome D2 replaces intermediate C1；
Elementary analysiss structure (molecular formula C77H54N2O2)：Theoretical value C, 88.99；H,5.24；N,2.70；O,3.08；Test Value：C,88.98；H,5.25；N,2.72；O,3.05.HPLC-MS：Material molecule amount is 1038.42, surveys molecular weight 1038.69。
Embodiment 20：The synthesis of compound 104：
Prepare by the synthetic method of compound 1 in embodiment 2, difference is to replace intermediate A 1 with intermediate A 4, in Mesosome E1 replaces intermediate C1；
Elementary analysiss structure (molecular formula C85H76N2)：Theoretical value C, 90.71；H,6.81；N,2.49；Test value：C, 90.72；H,6.80；N,2.48.HPLC-MS：Material molecule amount is 1124.60, surveys molecular weight 1124.97.
Embodiment 21：The synthesis of compound 112：
Prepare by the synthetic method of compound 18 in embodiment 6, difference is to replace intermediate C1 with intermediate C11；
Elementary analysiss structure (molecular formula C67H68N2)：Theoretical value C, 89.29；H,7.60；N,3.11；Test value：C, 89.30；H,7.60；N,3.10.HPLC-MS：Material molecule amount is 900.54, surveys molecular weight 900.54.
Embodiment 22：The synthesis of compound 124：
Prepare by the synthetic method of compound 18 in embodiment 6, difference is to replace intermediate C1 with intermediate C12；
Elementary analysiss structure (molecular formula C69H56N2)：Theoretical value C, 90.75；H,6.18；N,3.07；Test value：C, 90.74；H,6.20；N,3.06.HPLC-MS：Material molecule amount is 912.44, surveys molecular weight 912.73.
Embodiment 23：The synthesis of compound 129：
Prepare by the synthetic method of compound 18 in embodiment 6, difference is to replace intermediate C1 with intermediate C13；
Elementary analysiss structure (molecular formula C71H48N6)：Theoretical value C, 86.56；H,4.91；N,8.53；Test value：C, 86.54；H,4.92；N,8.54.HPLC-MS：Material molecule amount is 984.39, surveys molecular weight 984.76.
Embodiment 24：The synthesis of compound 137：
Prepare by the synthetic method of compound 20 in embodiment 7, difference is to replace intermediate B 1 with intermediate B 3；
Elementary analysiss structure (molecular formula C59H52N2)：Theoretical value C, 89.81；H,6.64；N,3.55；Test value：C, 89.80；H,6.63；N,3.57.HPLC-MS：Material molecule amount is 788.41, surveys molecular weight 788.78.
Embodiment 25：The synthesis of compound 143：
Prepare by the synthetic method of compound 18 in embodiment 6, difference is to replace intermediate C1 with intermediate E 2；
Elementary analysiss structure (molecular formula C57H44N2)：Theoretical value C, 90.44；H,5.86；N,3.70；Test value：C, 90.45；H,5.84；N,3.71.HPLC-MS：Material molecule amount is 756.35, surveys molecular weight 756.66.
Embodiment 26：The synthesis of compound 167：
1) in the there-necked flask of 250ml, under leading to nitrogen protection, 0.01mol intermediate Bs 1,0.012mol intermediate are added The stirring mixing of C3,150ml toluene, is subsequently adding 0.03mol sodium tert-butoxides, and 5 × 10-5molPd2(dba)3, 5 × 10-5The uncles of mol tri- Butyl phosphine, is heated to 105 DEG C, and back flow reaction 24 hours, sample point plate shows remaining without bromo-derivative, and reaction is complete；Natural cooling To room temperature, filter, filtrate carries out vacuum rotary steam to without fraction (- 0.09MPa, 85 DEG C), crosses neutral silica gel post, obtains middle product Thing, HPLC purity 99.8%, yield 65.3%；
Elementary analysiss structure (molecular formula C43H34BrN)：Theoretical value C, 80.12；H,5.32；Br,12.40；N,2.17；Survey Examination value：C,80.11；H,5.31；Br,12.40；N,2.18.HPLC-MS：Material molecule amount is 643.19, surveys molecular weight 643.52。
2) in the there-necked flask of 250ml, under leading to nitrogen protection, 0.005mol intermediate products, 0.006mol intermediate are added The stirring mixing of E3,150ml toluene, is subsequently adding 0.015mol sodium tert-butoxides, and 2.5 × 10-5molPd2(dba)3, 2.5 × 10- 5Mol tri-butyl phosphines, are heated to 105 DEG C, and back flow reaction 24 hours, sample point plate shows remaining without bromo-derivative, and reaction is complete； Room temperature is naturally cooled to, is filtered, filtrate carries out vacuum rotary steam (- 0.09MPa, 85 DEG C), cross neutral silica gel post, obtain target product Thing, HPLC purity 99.6%, yield 68.8%；
Elementary analysiss structure (molecular formula C64H50N2O2)：Theoretical value C, 87.44；H,5.73；N,3.19；O,3.64；Test Value：C,87.43；H,5.72；N,3.20；O,3.65.HPLC-MS：Material molecule amount is 878.39, surveys molecular weight 878.77.
Embodiment 27：The synthesis of compound 172：
Prepare by the synthetic method of compound 18 in embodiment 6, difference is to replace intermediate C1 with intermediate C14；
Elementary analysiss structure (molecular formula C59H52N2)：Theoretical value C, 89.81；H,6.64；N,3.55；Test value：C, 89.82；H,6.62；N,3.56.HPLC-MS：Material molecule amount is 788.41, surveys molecular weight 788.88.
The compounds of this invention can be used as luminescent layer dopant material, to the compounds of this invention 1,3,4,13,18,20, 23rd, 35,36,37,39,49,51,59,112,124,143,172 and control compounds BDI carry out hot property, luminescent spectrum and The test of HOMO energy levels, test result is as shown in table 4.
Table 4
Note：Vitrification point Tg is by differential scanning calorimetry (DSC, German Nai Chi companies DSC204F1 differential scanning calorimetries Instrument) determine, 10 DEG C/min of heating rate；Thermal weight loss temperature Td is in nitrogen atmosphere weightless 1% temperature, public in Japanese Shimadzu It is measured on the TGA-50H thermogravimetric analyzers of department, nitrogen flow is 20mL/min；λPLIt is sample solution fluorescence emission wavelengths, General health SR-3 spectroradiometer is opened up using Japan to determine；Highest occupied molecular orbital HOMO energy levels are ionization energy test systems (IPS-3) test, test as atmospheric environment.
From upper table data, the compounds of this invention has higher heat stability, and appropriate HOMO energy levels are suitable as The dopant material of luminescent layer；Meanwhile, the compounds of this invention has suitable luminescent spectrum so that using the compounds of this invention conduct The OLED efficiency of emitting layer material and life-span get a promotion.
The compounds of this invention is described in detail below by way of device embodiments 1~23 and device comparative example 1~2 to combine in device In application effect.Device embodiments of the present invention 2~23, device comparative example 1~2 device compared with device embodiments 1 The processing technology of part is identical, and employed identical baseplate material and electrode material, except that, the layer of device Stack structure, collocation material and thicknesses of layers are different.Device stack structure is as shown in table 5, the structural formula of critical materialses used As shown in table 6, the performance test results of each device are shown in Table 7.
Device embodiments 1：Device stack structure is illustrated shown in Fig. 1 such as device architecture：
The device includes successively from bottom to up (the thickness of ito anode layer 2：150nm), (thickness of hole injection layer 3：10nm, material Material：HI1), (thickness of hole transmission layer 4：70nm, material：HT6), (thickness of luminescent layer 6：25nm, material：BH1 and compound 1 are pressed Weight compares 95：5 blendings constitute), (thickness of electron transfer layer 8：35nm, material：ET2 and EI1, mass ratio 1:And Al (thickness 1)： 80nm)。
Concrete preparation process is as follows：
1st, ito anode layer 2 (thickness is 150nm) is washed；The washing is particularly preferably to carry out neutralizing treatment, pure successively Carry out ultraviolet-ozone after water washing, drying to wash to remove the organic residue on transparent ITO surfaces；
2nd, on the ito anode layer 2 after the washing, using vacuum deposition apparatus, hole injection layer, hole injection are deposited with Layer material uses HI1；The preferred thickness of the hole injection layer is 10nm；This layer is used as the hole injection layer 3 in device architecture；
3rd, on hole injection layer 3, by vacuum evaporation mode, hole transmission layer is deposited with, hole transport layer material is used HT6；The preferred thickness of the hole transmission layer is 70nm, and this layer is used as the hole transmission layer 4 in device architecture；
4th, on hole transmission layer 4, by vacuum evaporation mode, luminescent layer 6 is deposited with, emitting layer material uses BH1 conducts Material of main part, compound 1 is 95 as dopant material, doping mass ratio：5；The preferred thickness of the luminescent layer is 25nm, this Layer is used as the luminescent layer 6 in device architecture；
5th, on luminescent layer 6, by vacuum evaporation mode, electron transfer layer 8 is deposited with, electron transport layer materials use ET2 With EI1 mixing and dopings, doping mass ratio is 1:1；The preferred thickness of the electron transfer layer is 35nm, and this layer is used as device architecture In electron transfer layer 8；
6th, on electron transfer layer 8, by vacuum evaporation mode, evaporation cathode aluminum (Al) layer；Negative electrode aluminum (Al) layer Preferred thickness is 80nm, and this layer is used for negative electrode reflection electrode layer 10；
As described above, complete after the making of OLED luminescent devices, to be coupled together on anode and negative electrode with known drive circuit, The I-E characteristic of the life-span of measurement device, luminescent spectrum and device.Test result is shown in Table 7.
Device embodiments 2：Device stack structure is illustrated shown in Fig. 1 such as device architecture：
The device includes successively from bottom to up successively (the thickness of ito anode layer 2：150nm), (thickness of hole injection layer 3： 10nm, material：HI1), (thickness of hole transmission layer 4：70nm, material：HT5), (thickness of luminescent layer 6：25nm, material：BH3 and change Compound 3 is by weight 93：7 blendings constitute), (thickness of electron transfer layer 8：35nm, material：ET2 and EI1, mass ratio 1:And Al 1) (thickness：80nm).
Device embodiments 3：Device stack structure is illustrated shown in Fig. 1 such as device architecture：
The device includes successively from bottom to up successively (the thickness of ito anode layer 2：150nm), (thickness of hole injection layer 3： 10nm, material：HI2), (thickness of hole transmission layer 4：70nm, material：HT4), (thickness of luminescent layer 6：25nm, material：BH2 and change Compound 4 is by weight 92：8 blendings constitute), (thickness of electron transfer layer 8：35nm, material：ET3 and EI1, mass ratio 1:1), electricity (the thickness of sub- implanted layer 9：1nm, material：) and Al (thickness LiN3：80nm).
Device embodiments 4：The device including device stack structure such as device architecture illustrates Fig. 1 institutes successively from bottom to up successively Show：
(the thickness of ito anode layer 2：150nm), (thickness of hole injection layer 3：10nm, material：HI1), hole transmission layer 4 is (thick Degree：50nm, material：HT3), (thickness of electronic barrier layer 5：20nm, material：EB2), (thickness of luminescent layer 6：25nm, material：BH3 With compound 13 by weight 94：6 blendings constitute), (thickness of electron transfer layer 8：35nm, material：ET3 and EI1, mass ratio 1: And Al (thickness 1)：80nm).
Device embodiments 5：The device including device stack structure such as device architecture illustrates Fig. 1 institutes successively from bottom to up successively Show：
(the thickness of ito anode layer 2：150nm), (thickness of hole injection layer 3：10nm, material：HI1), hole transmission layer 4 is (thick Degree：50nm, material：HT5), (thickness of electronic barrier layer 5：20nm, material：HT6), (thickness of luminescent layer 6：25nm, material：BH1 With compound 18 by weight 93：7 blendings constitute), (thickness of electron transfer layer 8：35nm, material：ET2 and EI1, mass ratio 1: And Al (thickness 1)：80nm).
Device embodiments 6：The device including device stack structure such as device architecture illustrates Fig. 1 institutes successively from bottom to up successively Show：
(the thickness of ito anode layer 2：150nm), (thickness of hole injection layer 3：10nm, material：HI1), hole transmission layer 4 is (thick Degree：50nm, material：HT5), (thickness of electronic barrier layer 5：20nm, material：HT6), (thickness of luminescent layer 6：25nm, material：BH1 With compound 20 by weight 93：7 blendings constitute), (thickness of electron transfer layer 8：35nm, material：ET2 and EI1, mass ratio 1: And Al (thickness 1)：80nm).
Device embodiments 7：Device stack structure is illustrated shown in Fig. 1 such as device architecture：
The device includes successively from bottom to up successively (the thickness of ito anode layer 2：150nm), (thickness of hole injection layer 3： 60nm, material：HI3 and HT3, in mass ratio 5:95 blendings constitute), (thickness of hole transmission layer 4：20nm, material：HT3), light 6 (thickness of layer：25nm, material：BH4 and compound 23 are by weight 90：10 blendings constitute), (thickness of electron transfer layer 8：35nm, Material：ET3), (thickness of electron injecting layer 9：1nm, material：) and Al (thickness Li：80nm).
Device embodiments 8：The device including device stack structure such as device architecture illustrates Fig. 1 institutes successively from bottom to up successively Show：
(the thickness of ito anode layer 2：150nm), (thickness of hole injection layer 3：10nm, material：HI1), hole transmission layer 4 is (thick Degree：50nm, material：HT5), (thickness of electronic barrier layer 5：20nm, material：HT6), (thickness of luminescent layer 6：25nm, material：BH1 With compound 35 by weight 88：12 blendings constitute), (thickness of electron transfer layer 8：35nm, material：ET2 and EI1, mass ratio 1: And Al (thickness 1)：80nm).
Device embodiments 9：Device stack structure is illustrated shown in Fig. 1 such as device architecture：
The device includes successively from bottom to up successively (the thickness of ito anode layer 2：150nm), (thickness of hole injection layer 3： 60nm, material：HI3 and HT2, in mass ratio 2:98 blendings constitute), (thickness of hole transmission layer 4：20nm, material：HT6), light 6 (thickness of layer：25nm, material：BH1 and compound 36 are by weight 95：5 blendings constitute), (thickness of electron transfer layer 8：35nm, Material：ET2 and EI1, mass ratio 1:And Al (thickness 1)：80nm).
Device embodiments 10：Device stack structure is illustrated shown in Fig. 1 such as device architecture：
The device includes successively from bottom to up successively (the thickness of ito anode layer 2：150nm), (thickness of hole injection layer 3： 60nm, material：HI4 and HT3, in mass ratio 5:95 blendings constitute), (thickness of hole transmission layer 4：20nm, material：HT6), light 6 (thickness of layer：25nm, material：BH2 and compound 37 are by weight 93：7 blendings constitute), (thickness of electron transfer layer 8：35nm, Material：ET4 and EI1, mass ratio 1:1), (thickness of electron injecting layer 9：1nm, material：) and Al (thickness LiF：80nm).
Device embodiments 11：Device stack structure is illustrated shown in Fig. 1 such as device architecture：
The device includes successively from bottom to up successively (the thickness of ito anode layer 2：150nm), (thickness of hole injection layer 3： 10nm, material：HI1), (thickness of hole transmission layer 4：50nm, material：HT6), (thickness of electronic barrier layer 5：20nm, material： EB1), (thickness of luminescent layer 6：25nm, material：BH3 and compound 39 are by weight 92：8 blendings are constituted), hole blocking layer 7 it is (thick Degree：20nm, material：HB1), (thickness of electron transfer layer 8：15nm, material：ET2 and EI1, mass ratio 1:And Al (thickness 1)： 80nm)。
Device embodiments 12：Device stack structure is illustrated shown in Fig. 1 such as device architecture：
The device includes successively from bottom to up successively (the thickness of ito anode layer 2：150nm), (thickness of hole injection layer 3： 50nm, material：HI5 and HT3, in mass ratio 5:95 blendings constitute), (thickness of hole transmission layer 4：20nm, material：HT5), electronics (the thickness of barrier layer 5：10nm, material：EB3), (thickness of luminescent layer 6：25nm, material：BH3 and compound 49 are by weight 90：10 Blending is constituted) (the thickness of/electron transfer layer 8：35nm, material：ET2 and EI1, mass ratio 1：1), (thickness of electron injecting layer 9： 1nm, material：Cs2CO3) and Al (thickness：80nm).
Device embodiments 13：Device stack structure is illustrated shown in Fig. 1 such as device architecture：
The device includes successively from bottom to up successively (the thickness of ito anode layer 2：150nm), (thickness of hole injection layer 3： 50nm, material：HI6 and HT4, in mass ratio 5:95 blendings constitute), (thickness of hole transmission layer 4：20nm, material：HT6), electronics (the thickness of barrier layer 5：10nm, material：EB2), (thickness of luminescent layer 6：25nm, material：BH3 and compound 51 are by weight 90：10 Blending constitute), (thickness of electron transfer layer 8：35nm, material：ET2 and EI1, mass ratio 1：1), (thickness of electron injecting layer 9： 1nm, material：) and Al (thickness EI1：80nm).
Device embodiments 14：Device stack structure is illustrated shown in Fig. 1 such as device architecture：
The device includes successively from bottom to up successively (the thickness of ito anode layer 2：150nm), (thickness of hole injection layer 3： 10nm, material：HI1), (thickness of hole transmission layer 4：50nm, material：HT3), (thickness of electronic barrier layer 5：20nm, material： EB1), (thickness of luminescent layer 6：25nm, material：BH3 and compound 59 are by weight 94：6 blendings are constituted), hole blocking layer 7 it is (thick Degree：25nm, material：HB1), (thickness of electron transfer layer 8：10nm, material：ET5), (thickness of electron injecting layer 9：1nm, material： ) and Al (thickness EI1：80nm).
Device embodiments 15：Device stack structure is illustrated shown in Fig. 1 such as device architecture：
The device includes successively from bottom to up successively (the thickness of ito anode layer 2：150nm), (thickness of hole injection layer 3： 60nm, material：HI3 and HT4, in mass ratio 2:98 blendings constitute), (thickness of hole transmission layer 4：20nm, material：HT6), light 6 (thickness of layer：25nm, material：BH4 and compound 112 are by weight 93：7 blendings constitute), (thickness of hole blocking layer 7：15nm, Material：HB1), (thickness of electron transfer layer 8：35nm, material：ET2 and EI1, mass ratio 1：And Al (thickness 1)：80nm).
Device embodiments 16：Device stack structure is illustrated shown in Fig. 1 such as device architecture：
The device includes successively from bottom to up successively (the thickness of ito anode layer 2：150nm), (thickness of hole injection layer 3： 50nm, material：HI5 and HT6, in mass ratio 5:95 blendings constitute), (thickness of hole transmission layer 4：20nm, material：HT6), electronics (the thickness of barrier layer 5：10nm, material：EB2), (thickness of luminescent layer 6：25nm, material：BH5 and compound 124 are by weight 95：5 Blending constitute), (thickness of hole blocking layer 7：15nm, material：HB1), (thickness of electron transfer layer 8：20nm, material：ET2 and EI1, mass ratio 1：1), (thickness of electron injecting layer 9：1nm, material：Li2) and Al (thickness CO3：80nm).
Device embodiments 17：Device stack structure is illustrated shown in Fig. 1 such as device architecture：
The device includes successively from bottom to up successively (the thickness of ito anode layer 2：150nm), (thickness of hole injection layer 3： 60nm, material：HI5 and HT3, in mass ratio 5:95 blendings constitute), (thickness of hole transmission layer 4：20nm, material：HT6), light 6 (thickness of layer：25nm, material：BH5 and compound 143 are by weight 95：5 blendings constitute), (thickness of hole blocking layer 7：15nm, Material：HB1), (thickness of electron transfer layer 8：20nm, material：ET6), (thickness of electron injecting layer 9：1nm, material：) and Al CsF (thickness：80nm).
Device embodiments 18：Device stack structure is illustrated shown in Fig. 1 such as device architecture：
The device includes successively from bottom to up successively (the thickness of ito anode layer 2：150nm), (thickness of hole injection layer 3： 50nm, material：HI5 and HT3, in mass ratio 5:95 blendings constitute), (thickness of hole transmission layer 4：20nm, material：HT6), electronics (the thickness of barrier layer 5：10nm, material：EB2), (thickness of luminescent layer 6：25nm, material：BH5 and compound 172 are by weight 94：6 Blending constitute), (thickness of electron transfer layer 8：35nm, material：ET2 and EI1, mass ratio 1：1), (thickness of electron injecting layer 9： 1nm, material：CsN3) and Al (thickness：80nm).
Device embodiments 19：Device stack structure is illustrated shown in Fig. 1 such as device architecture：
The device includes successively from bottom to up successively (the thickness of ito anode layer 2：150nm), (thickness of hole injection layer 3： 10nm, material：HI1), (thickness of hole transmission layer 4：50nm, material：HT5), (thickness of electronic barrier layer 5：20nm, material： HT6), (thickness of luminescent layer 6：25nm, material：BH4 and compound 18 are by weight 93：7 blendings are constituted), electron transfer layer 8 it is (thick Degree：35nm, material：ET2 and EI1, mass ratio 1：And Al (thickness 1)：80nm).
Device embodiments 20：Device stack structure is illustrated shown in Fig. 1 such as device architecture：
The device includes successively from bottom to up successively (the thickness of ito anode layer 2：150nm), (thickness of hole injection layer 3： 60nm, material：HI4 and HT3, in mass ratio 5:95 blendings constitute), (thickness of hole transmission layer 4：20nm, material：HT6), light 6 (thickness of layer：25nm, material：BH4 and compound 20 are by weight 88：12 blendings constitute), (thickness of electron transfer layer 8：35nm, Material：ET7 and EI1, mass ratio 1:1), (thickness of electron injecting layer 9：1nm, material：) and Al (thickness LiF：80nm).
Device embodiments 21：Device stack structure is illustrated shown in Fig. 1 such as device architecture：
The device includes successively from bottom to up successively (the thickness of ito anode layer 2：150nm), (thickness of hole injection layer 3： 10nm, material：HI1), (thickness of hole transmission layer 4：50nm, material：HT5), (thickness of electronic barrier layer 5：20nm, material： HT6), (thickness of luminescent layer 6：25nm, material：BH4 and compound 35 are by weight 85：15 blendings constitute), electron transfer layer 8 (thickness：35nm, material：ET3 and EI1, mass ratio 1:And Al (thickness 1)：80nm).
Device embodiments 22：Device stack structure is illustrated shown in Fig. 1 such as device architecture：
The device includes successively from bottom to up successively (the thickness of ito anode layer 2：150nm), (thickness of hole injection layer 3： 60nm, material：HI5 and HT3, in mass ratio 5:95 blendings constitute), (thickness of hole transmission layer 4：20nm, material：HT6), light 6 (thickness of layer：25nm, material：BH5 and compound 172 are by weight 95：5 blendings constitute), (thickness of hole blocking layer 7：15nm, Material：HB1), (thickness of electron transfer layer 8：20nm, material：ET6), (thickness of electron injecting layer 9：1nm, material：) and Al CsF (thickness：80nm).
Device comparative example 23：Device stack structure is illustrated shown in Fig. 1 such as device architecture：
The device includes successively from bottom to up successively (the thickness of ito anode layer 2：150nm), (thickness of hole injection layer 3： 10nm, material：HT1), (thickness of hole transmission layer 4：50nm, material：HT5), (thickness of electronic barrier layer 5：20nm, material： HT6), (thickness of luminescent layer 6：25nm, material：CBP and compound 51 are by weight 95：5 blendings are constituted), electron transfer layer 8 it is (thick Degree：35nm, material：ET2 and EI1, mass ratio 1:And Al (thickness 1)：80nm).
Device comparative example 1：Device stack structure is illustrated shown in Fig. 1 such as device architecture：
The device includes successively from bottom to up successively (the thickness of ito anode layer 2：150nm), (thickness of hole injection layer 3： 10nm, material：MoO3), (thickness of hole transmission layer 4：40nm, material：TAPC), (thickness of luminescent layer 6：30nm, material：CBP and Compound BDI is by weight 97：3 blendings constitute), (thickness of electron transfer layer 8：40nm, material：TPBI), electron injecting layer 9 (thickness：1nm, material：) and Al (thickness LiF：80nm).
Device comparative example 2：Device stack structure is illustrated shown in Fig. 1 such as device architecture：
The device includes successively from bottom to up successively (the thickness of ito anode layer 2：150nm), (thickness of hole injection layer 3： 10nm, material：HT1), (thickness of hole transmission layer 4：50nm, material：HT5), (thickness of electronic barrier layer 5：20nm, material： HT6), (thickness of luminescent layer 6：25nm, material：BH1 and compound BDI is by weight 97：3 blendings constitute), electron transfer layer 8 (thickness：35nm, material：ET2 and EI1, mass ratio 1:And Al (thickness 1)：80nm).
The OLED is characterized by standard method, from current/voltage/luminous density characteristic line that Lambert emission characteristic is presented Calculate, and the measurement life-span.Device test data is as shown in table 7.
Table 5
Table 6
Table 7
Table 7 summarizes the OLED in 1000cd/m2Voltage needed for brightness, the external quantum efficiency for reaching；And In 1000cd/m2LT90 Decays under brightness.
The comparative device comparative example 1 of device comparative example 2, has changed the material adapted of the present invention, and device realizes low-voltage, height Efficiency and long-life effect；Device embodiments 1-23 comparative devices comparative example 2, changes the luminescent layer dopant material of the present invention, and By the combination of materials of the present invention into after laminated device, device voltage is reduced, and external quantum efficiency and life-span are highly improved.
Further material of the present invention is capable of achieving to be used without concentration quenching effect, holding high efficiency during high-concentration dopant.Table 8 For the embodiment device architecture of variable concentrations：
Table 8
Device test data is as shown in table 9：
Table 9
The device architecture that device embodiments 24~26 are arranged in pairs or groups for material of the present invention and screening material, and device comparative example phase Than under high-concentration dopant, device efficiency is not reduced, and does not have concentration quenching effect.
OLED prepared by further material of the present invention can be kept for the long-life at high temperature, by device embodiments 1~26 and device comparative example 1~4 carry out high temperature driven life test at 85 DEG C, acquired results are as shown in table 10.
Table 10
Knowable to the data of table 10, device embodiments 1~26 are the device architecture that material of the present invention and screening material are arranged in pairs or groups, Compare with device comparative example, under high temperature, the OLED that the present invention is provided has and drive well the life-span.
To sum up, presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention Within god and principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.

Claims (13)

1. a kind of organic electroluminescence device of the compound containing with dibenzocycloheptene as core, the device includes that hole passes Defeated layer, luminescent layer, electron transfer layer, it is characterised in that the device emitting layer material includes that containing dibenzocycloheptene be core Compound, shown in the structural formula of compound such as formula (1)：
In formula (1), R1、R2Independently be expressed as substituted or unsubstituted C6-40Aryl, substituted or unsubstituted 3 yuan of rings To one kind of 40 membered ring heteroaryls；R1With R2Between dotted line represent R1With R2Cyclization or not cyclization can be connected；R1、R2It is identical or Person is different；
R3、R4Independently be expressed as formula (2), formula (3) or structure shown in formula (4)；
In formula (2), R5、R6Separately it is expressed as substituted or unsubstituted C6-40Aryl, substituted or unsubstituted 3 yuan of rings One kind into 40 membered ring heteroaryls；R5、R6Identical or difference；
In formula (4), X1It is expressed as oxygen atom, sulphur atom, C1-10Alkylidene, C that straight chained alkyl replaces1-10Branched alkyl replaces Alkylidene, the tertiary amine groups that replace of the alkylidene that replaces of aryl, alkyl-substituted tertiary amine groups or aryl in one kind；
In formula (3) and formula (4), R7、R8Independently be expressed as hydrogen atom or structure shown in formula (5)；
Wherein, a is selected fromX2、X3Independently be expressed as oxygen atom, sulphur atom, C1-10Straight chain alkane Alkylidene, C that base replaces1-10Alkylidene, the alkylidene of aryl replacement, alkyl-substituted tertiary amine groups or virtue that branched alkyl replaces One kind in the tertiary amine groups that base replaces；Structure shown in formula (5) passes through CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL4-CL5Key, CL‘1-CL’2Key, CL‘2-CL’3Key, CL‘3-CL’4Key or CL‘4-CL’5Key and formula (3) or formula (4) connection.
2. organic electroluminescence device according to claim 1, it is characterised in that R in the formula (1)1、R2And formula (2) R in5、R6Structure being expressed as independently：
In any one.
3. organic electroluminescence device according to claim 1, it is characterised in that the representation of the formula (3) is：
In any one.
4. organic electroluminescence device according to claim 1, it is characterised in that the representation of the formula (4) is：
Any one.
5. organic electroluminescence device according to claim 1, it is characterised in that the concrete structure formula of the compound is：
In any one.
6. organic electroluminescence device according to claim 1, it is characterised in that described with dibenzocycloheptene as core Compounds process for production thereof is：
Work as R3And R4When identical, with following reaction equation：
Specifically include following steps：
1) by intermediate compound I and R3- H toluene dissolves, wherein, the intermediate compound I and R3The mol ratio of-H is 1:(2.0~3.0)；
2) Pd is added in above-mentioned reaction system2(dba)3, tri-butyl phosphine, sodium tert-butoxide；The Pd2(dba)3With intermediate compound I Mol ratio be (0.006~0.02):1, the tri-butyl phosphine is (0.006~0.02) with the mol ratio of intermediate compound I:1, institute It is (3.0~5.0) that sodium tert-butoxide is stated with the mol ratio of intermediate compound I:1；
3) under the protection of noble gases, above-mentioned mixed solution is reacted into 10~24h under 95~110 DEG C of temperature conditionss, from Room temperature, filtering reacting solution are so cooled to, filtrate is rotated to solvent-free, crosses neutral silica gel post, obtains target product；
Work as R3And R4When differing, with following reaction equation：
Specifically include following steps：
1) by intermediate compound I and R3- H toluene dissolves, wherein, the intermediate compound I and R3The mol ratio of-H is 1:(1.2~2.0)；
2) Pd is added in the reaction system in 1)2(dba)3, tri-butyl phosphine, sodium tert-butoxide；；The Pd2(dba)3With centre The mol ratio of body I is (0.006~0.02):1, the tri-butyl phosphine is (0.006~0.02) with the mol ratio of intermediate compound I: 1, the sodium tert-butoxide is (2.0~3.0) with the mol ratio of intermediate compound I:1；
3) under the protection of noble gases, above-mentioned mixed solution is reacted into 10~24h under 95~110 DEG C of temperature conditionss, from Room temperature, and filtering reacting solution are so cooled to, filtrate is rotated to solvent-free, crosses neutral silica gel post, obtains intermediate product；
4) by intermediate product and R4- H toluene dissolves, wherein, the intermediate product and R4The mol ratio of-H is 1:(1.2~ 2.0)；
5) Pd is added in the reaction system in 4)2(dba)3, tri-butyl phosphine, sodium tert-butoxide；The Pd2(dba)3With middle product The mol ratio of thing is (0.006~0.02):1, the tri-butyl phosphine is (0.006~0.02) with the mol ratio of intermediate product: 1, the sodium tert-butoxide is (2.0~3.0) with the mol ratio of intermediate product:1；
6) under the protection of noble gases, above-mentioned mixed solution is reacted into 10~24h under 95~110 DEG C of temperature conditionss, from Room temperature, and filtering reacting solution are so cooled to, filtrate is rotated to solvent-free, crosses neutral silica gel post, obtains target product.
7. organic electroluminescence device according to claim 1, it is characterised in that the organic electroluminescence device includes Hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron transfer layer, the organic electroluminescence device it is luminous Layer material includes the compound with dibenzocycloheptene as core.
8. organic electroluminescence device according to claim 7, it is characterised in that described with dibenzocycloheptene as core Dopant material of the compound as luminescent layer；The material of main part of the luminescent layer is the compound containing anthryl, described to contain anthracene Shown in the structure of the compound of base such as formula (6)：
In formula (6), B1-B8Independently be expressed as hydrogen atom, C1-30Alkyl or alcoxyl that straight or branched alkyl replaces Base, substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 3 yuan of rings are to 30 membered ring heteroaryls；B9、B10Independently represent For substituted or unsubstituted C6-30Aryl, substituted or unsubstituted 3 yuan to 30 unit's heteroaryls.
9. organic electroluminescence device according to claim 7, it is characterised in that the material of the hole transmission layer be containing There is the compound of triarylamine group, shown in the structure such as formula (7) of the compound containing triarylamine group：
In formula (7), D1-D3The substituted or unsubstituted C of expression independently6-30Aryl, substituted or unsubstituted 3 yuan of rings are extremely 50 membered ring heteroaryls；D1-D3Identical or difference.
10. organic electroluminescence device according to claim 7, it is characterised in that the material of the electron transfer layer is One kind in general formula (8), (9), (10), (11), material shown in (12)：
E in formula (8), formula (9), formula (10), formula (11), formula (12)1-E10It is respectively and independently selected from hydrogen, C1-30Straight chain or Alkyl or alkoxyl, substituted or unsubstituted C that branched alkyl replaces6-40Aryl, substituted or unsubstituted 3 yuan of rings are to 30 yuan of rings Heteroaryl, and E1-E10It is asynchronously hydrogen.
11. organic electroluminescence devices according to claim 7, it is characterised in that under the hole injection layer material is One kind in array structure formula (13), (14), material shown in (15)：
In formula (13), F1-F3The substituted or unsubstituted C of expression independently6-30Aryl, substituted or unsubstituted 3 yuan to 30 Unit's heteroaryl；F1-F3Identical or difference；
In formula (14), formula (15), G1-G6Expression hydrogen independently, itrile group, halogen, amide groups, alkoxyl, ester group, nitre Base, C1-30Carbon atom, substituted or unsubstituted C that straight or branched alkyl replaces6-30Aryl, 3 yuan of rings to 30 membered ring heteroaryls and G1-G6It is asynchronously hydrogen.
12. organic electroluminescence devices according to claim 7, it is characterised in that the electron injecting layer material be lithium, One kind in lithium salts or cesium salt.
Organic electroluminescence device described in a kind of 13. any one of claim 1 to 12 is applied to prepare OLED illuminations or display surface Plate.
CN201611206415.XA 2016-12-23 2016-12-23 Organic electroluminescent device containing chemical compound with dibenzocycloheptene as its core and the application thereof Pending CN106684254A (en)

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CN110343049A (en) * 2018-04-04 2019-10-18 江苏三月光电科技有限公司 It is a kind of using spiral shell dibenzocycloheptene fluorenes as the organic compound of skeleton and its application
CN110655498A (en) * 2018-06-29 2020-01-07 江苏三月光电科技有限公司 Compound with dibenzosuberene as central skeleton and application thereof
CN112321644A (en) * 2019-12-24 2021-02-05 广东聚华印刷显示技术有限公司 Spiro dibenzosuberene phosphine oxide compound and application thereof

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KR20110041730A (en) * 2009-10-16 2011-04-22 에스에프씨 주식회사 Fused aromatic compound and organic electroluminescent device using the same
CN105238389A (en) * 2015-10-12 2016-01-13 中节能万润股份有限公司 Novel organic electroluminescent material and use thereof
CN106467468A (en) * 2016-06-13 2017-03-01 江苏三月光电科技有限公司 A kind of organic compound with dibenzo heptene structure and its application

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KR20110041730A (en) * 2009-10-16 2011-04-22 에스에프씨 주식회사 Fused aromatic compound and organic electroluminescent device using the same
CN105238389A (en) * 2015-10-12 2016-01-13 中节能万润股份有限公司 Novel organic electroluminescent material and use thereof
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CN107216279A (en) * 2017-06-12 2017-09-29 江苏三月光电科技有限公司 A kind of compound as core using dibenzocycloheptene and its application on organic electroluminescence device
CN110343049A (en) * 2018-04-04 2019-10-18 江苏三月光电科技有限公司 It is a kind of using spiral shell dibenzocycloheptene fluorenes as the organic compound of skeleton and its application
CN110343049B (en) * 2018-04-04 2022-09-09 江苏三月科技股份有限公司 Organic compound with spiro dibenzosuberene fluorene as skeleton and application thereof
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CN112321644A (en) * 2019-12-24 2021-02-05 广东聚华印刷显示技术有限公司 Spiro dibenzosuberene phosphine oxide compound and application thereof

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